Azo compounds and material colored therewith



Patented Nov. 12, 1940 i Q or 1,

(UNITED STATES PATENT" oFricE,

James G. McNally and Joseph B. Dickey; Rochester, N. Y assignors to Eastman Kodak Company, Rochester, N, Y., a. corporation of New Jersey a.

No Drawing. Ap lication July 1, 1939,

Serial No. 282,528

13 Claims. (Cl. 260-15'2) This invention relates to the art of dyeing or wherein R represents the residue of an aromatic coloring. More particularly, it relates to azo dye nucleus, Z represents a member selectedfrom compounds and the application of the nuclear the group consisting of a sulfur atom, a S=O non-sulfonated azo dye compounds for the coloragroup anda a l v tion of organic derivatives of cellulose, pzarticu- H O 5 larly textile materials made of or containing an p organic derivative of cellulose by dyeing, printing, g *K stenciling, or like methods. I f p 0 Organic derivatives of cellulose are character-. l W v I 1o ized by an indifferent afiinity for the usual cotton group, B represents theresidue of an aryl nucleus and W001 y especially the Ordinary te of the benzene series containing but one benzene soluble dyes. Because of this, it has loeen necesnucleus and wherein the nitrogen atom shown sary to develop new dye, compounds suitablefor and Z are attachedlto saidaryl nucleus B in para the dyeing or coloration of materials suchas teX- and meta position, respectively, to the azo bond, 16 tile materials .made of or containing an organic B1 representsv the residue of, an aryl nucleus of derivative of cellulose. It is, accordingly, an obthe benzene series containing but one ioen'zene ject of our invention to provide a neW C ass O nucleus joinedjto the nucleus-shown through adazo dyes suitable for the dyeing or coloration of jacem; bo t m d X d Y eachreprer organic derivatives of cellulose. sents a memberselectd from-thegroup consisteJ Another object of our invention is 130 provide a 111g of hydrogen, an alkyl group, 3, 1 allyl group, 20

process for the dyeing or coloration of organic an and group'and a cycloalkyl group. derivatives of cellulose. A furt er O jec is 10 It will beunderstood that alkylgas used herein, provide a process for the coloration of organic unless otherwise indicated, includes not only un-i derivatives of cellulose in which the dye or dyes substituted alkyl groups such :as a methyl group,

are applied directly to the material undergoing an ethyl group, a propyl group or a b tyl group coloration from an aqueous suspension? A still b t a b tit t d ,alkyl groups ch as fl-hyfurther object is to produce dyeings on organic d th p-hydroxypropyl fifl'mydroxypmpyl, derivatives of cellulose which are of good fastness cemethoxyethyl or ,B-ethoxyethyl, for example. to light andwashing. l Illustrative of cycloalkyl may be mentioned cyclo- Typical organic derivatives of cellulose include butyl and cyclohexyl. 30

the hydrolyzed as well as the unhydrolyzed cel- The azo dye compounds of our invention can lulose organic acid esters, such as cellulose aceb e red by diazotizing primary ro ati tate; cellulose formate, cellulose propionate or amine nd coupling th diazonium o ound e ose uty e y y d s Well as obtained with a coupling component selected the, unhydrolyzed mixed organic acid esters of from the group consisting of coupling components 3 cellulose, such as cellulose acetate-propionate, represented b th genera] formula cellulose acetate-butyrate, land the cellulose 1 v l ethers, such as methyl cellulose, ethyl cellulose or z benzyl cellulose. While our invention will be a i j M v 40 illustrated more particularly in connection with I B 40 the coloration of cellulose acetate, a material to Q which the invention is especially adapted, it will N" v x, it be understood that it applies to the coloration of f other organic derivatives of cellulose such as I those just mentioned. and a a V 45 The azo dye compounds of our invention con- I 1 I sist of the azo compounds represented by the H general formulae: a 1

' I I OH: H Y j /H Z/\0 I I CHT1' "50 N--C l a l r v a RN=N--'-B l X and R N N N Y Z 2-- H2 5Q B1 5 B1 represents the residue of an aryl nucleus of the wherein Z represents a sulfur atom, a S=O group anda group, 3' represents the residue of an aryl nucleus of the benzene series and wherein Z and the nitrogen atom shown attached to B are joined to adjacent carbon atoms of saidaryl nucleus B,

benzene series joined to the nucleus shown through adjacent carbon atoms, and X and Y group consisting of hydrogen, an alkyl group, an allyl group, an aryl group and a cycloalkyl group.

The aryl nuclei B and B1 can contain various substituents as clearly shown hereinafter. Illustrative of such substituents can be mentioned an alkyl group, an alkoxy group such as me-thoxy, ethoxy, propoxy, fl-methoxyethoxy or p-ethoxyethoxy,a halogen atom such as bromine, chlorine utility for the colonation of organic derivatives of cellulose but are of utility for the dyeing of cotton,wool and silk. These latter compounds may beprepared by sulfonation of the unsulfonated azo dye compounds or by prior sulfonation of the intermediates employed in their preparation. Generally speaking, when the azo dye compounds of our invention are to be used for the colonation of organic derivatives of cellulose, it is advantageous that they do not contain a nuclear free carboxylic acid group. Dyeings of good fastness to light and washing of various shades can be obtained when employing the dye compounds of our invention. For the dyeing of organic derivatives of cellulose, compounds wherein B is an aryl nucleus of the benzene series are generally advantageous.

The following examples illustrate the preparation of the azo dye compounds of our invention.

Example 1 are dissolved in a dilute hydrochloric acid solution. The resulting solution is cooled to a temperature approximating 0-10 C. and the diazo solution prepared as described above is added with stirring. After addition of the diazo solution, the mixture is allowed to stand for a short time after which it is made neutral to Congo each represents a member selected from the i grams of CH3 N-CH:

CHzCHaOH 26.8 grams of CHQCHOHGHIOH and 26.9 grams of OCH:

N-CH:

O CH:

respectively, for 23.5 grams of in the above example, other dye compounds within the scope of our invention can be prepared.

Similarly, 17.3 grams of 1-amino-2-chloro-4- nitrobenzene, 21.7 grams of 1-amino-2-bromo-4- nitrobenzene, 16.8 grams of 1-amino-2-methoxy- 4-nitrobenzene and 18 grams of 4-amino-3-nitrophenylmethylketone can be diazotized and each of the diazonium compounds resulting can be coupled with each of the coupling components above described to obtain dye compounds of our invention.

Example 2 29.5 grams of CHaCHzSOaNa are dissolved in water. The resulting solution is cooled to a temperature approximating 0-10 C. and the diazonium compound resulting from the diazotization of 12.8 grams of o-chloroaniline are added with stirring. Followingthe addition of the -diazotized o-chloroam'line, the mixture is slowly made neutral to litmus by the addition'of sodium carbonate. Upon completion of the coupling reaction which takes place, the dye compound formed is precipitated out by the addition of sodium chloride, recovered by filtration, and dried. 1

31.1 grams of OHzOHaO S OaNa may be substituted for the coupling component of the above example to obtain a dye compound of our invention. Similarly, 13.5 grams of p-aminoacetophenone may be diazotized and the diazonium compound resulting canbe coupled with each of the coupling components just mentioned to obtain dye compounds of our invention.

\ Example 3 18.3 grams of 1-amin0-2,4-dinitrobenzene are diazotized in known fashion and the diazonium compound resulting is coupled with 20.1 grams of Coupling and recovery of the dye compound formed may be carried out in accordance with the method described in Example 1. The dye compound thus obtained colors cellulose acetate silk a purple shade.

21.5 grams of C-CH:

HN CH2 24.5 grams of and 27.5 grams of CHzCHzOH N 04cm can be substituted for the coupling component of the example to obtain dye compounds of our invention. Similarly, 21.8 grams of Lamina-2,4- dinitro-G-chlorobenzene and 26.2 grams of 1- amino-ZA-dinitro-B-bromobenzene can be diazotized and the diazonium compounds obtained coupled with each of the coupling components is dissolved in dry pyridine and treated with .1 gram mole of v The reaction is completed by warming. Following completion of the reaction, aqueous sodium carbonate is added and the reaction product is worked up in known fashion. The dye come pound obtained has the formula:

OCH;

O 0N9. I (3E2. l

N=N 'N\ A OOHa cmGHZQHZ-O P O-O 0 ONE and colors cellulose acetate silk, wool and silk a red shade. I

Eazample 5 20.7 grams of p-aminoazobenzene are diazotized and the diazonium compound obtained is coupledwith 34.7 grams of The diazotization reaction may be carried out as, described in Example 1 while the coupling reaction and recovery of the dye compound formed may be carried out as described in Example 2.

The dye compound obtained colors cellulose acetate silk, wool and silk a rubine shade.

Example 6 18.6 grams of 5-nitro-Z-aminobenzenesulfonic acid are diazotized in known fashion and the diazoniuni compound obtained is coupled with 36 grams of mentioned in this example to obtain dye compounds of our invention.

The coupling reaction may be carried out in accordance with the general method described in Example 1. The dye compound obtained colors wool and silk a violet shade.

Example 7 13.8 grams of p-nitroaniline are diazotized and the diazonium compound obtained is coupled with 16.7 grams of The diazotization, coupling and recovery of the dye compound formed may be carried out as described in Example 1. The dye compound obtained colors cellulose acetate silk a red shade.

18.3 grams of can be substituted for the coupling compound of the above example to obtain a dye compound which similarly colors cellulose acetate silk 2. red shade.

Example 8 Coupling and recovery of the dye compound may be carried out as described in Example 1. The dye compound obtained colors cellulose acetate silk a rubine shade.

21.1 grams of r can be substituted for the coupling component of the above example to obtain a dye compound which similarly colors cellulose acetate silk a rubine shade.

Coupling components identical with those disclosed in Examples 1, 2, 3, 5 and 6, except that the sulfur atom in the ring joined to the benzene or naphthalene nucleus is replaced by a S=O group or a group, can be coupled with the diazo components shown in these examples to obtain dye compounds of analogous structure which possess generally similar dyeing properties as the corresponding dyes of said examples. Similarly, coupling components identical with those dis closed in the tabulation hereinafter, except for the difference above noted, can be coupled with the diazonium derivatives of the amines listed in the tabulation to obtain dye compounds which possess generally similar dyeing properties as the corresponding dyes of said tabulation. Again, an azo compound identical with that undergoing treatment in Example 4, except that the sulfur atoms joined to the naphthyl nuclei are replaced by S=O or groups, can be similarly treated to obtain dye compounds of analogous structure and dyeing properties. It will be understood of course that any of the diazo components disclosed herein may be coupled with any of the coupling components disclosed herein to'obtain dye compounds included within the scope of our invention. The specific dye compounds disclosed herein are intended to be illustrative and not limitative of the invention.

The following tabulation further illustrates the compounds included within the scope of our invention together with the. color they produce on cellulose acetate silk. -The compounds indicated below may be prepared by diazotizing the amines listed under the heading Amine and N coupling the diazonium compounds obtained with CH the compounds specified in the column entitled I Coupling component." The diazotization and /CH2 coupling reactions may, for example, be carried out following the general procedure described in Examples 1 to 8, inclusive.

Color on Amine Coupling component cellulosgilgcetato 0: -Halo Ii 9 (1 p m n 1% (i111: Yellow. CH:

Dn (2) (3H3 (EH, Do. CH2

Amine W Coupling component Color on cellulose cetate l-amino-2,4-dinitro-6-halobenzene Coupling components 1-10 1-amino- 2,4 -dinitro*lhalobenzene.

1-a.mino-2-i1itro-4-chlorobenzene.

1-amino-2,4-diuitronaphthaleue r? n 1-amino-2,4,6-trinitrobenzene do CH: '1-am1no-2A-dinitrobenzene (11) H/ /CH: S

C-(JH: II I OH:

D0 (13) CHzCHzOH /H CH2 N D0 14 v CHzQHOHCHzOH N CH:

Do I (15) /CHzOHzSOsNa g N "(3H1 /0H2 D0 (16) (I3H=CHCH| N CH:

JH| S Coupling Components 11-16 (18) cylcohexyl Violet to red-- dish-blue. Do. Reddish blue to blue.

Purple.

Violet.

Greeuish-blue.

Purple to greenish blue.

Violet.

Diazotized 5-nitro-Z-aminobenzenesulfonic acid may be coupled with each of the coupling components numbered 1 to 10 above to obtain dyes which yield red shades on wool and silk. This same diazonium compound may be coupled with each of the coupling components numbered 11 to 18 to obtain dye compounds which are suitable for the coloration of wool and silk and which yield various shades thereon.

In order that the preparation of the azo compounds of our invention may be clearly understood the preparation of a number of intermediate compounds employed in their manufacture is given hereinafter.

/H (J-CH2 101' example, can be prepared by reducing in accordance with the general procedure described in Berichte der Deutschen Chemischen Gesellschaft, vol. 31, pages 752-758 (1897). The desired compound can be purified by distillation under reduced pressure. In a similar manner,

' can be prepared by reducing Similarly,

can be prepared by reducing Thus, compounds having the general formulae:

and i H 1 7 f N /CH2 h wherein B, B1 and X have the meaning previously assigned to them can be prepared by reducing compounds having the general formulae:

s-oi=ncx and s-om-d-x B1 I wherein B, B1 and X have the meaning previously assigned to them. These latter compounds can be prepared after the general method set forth in Liebigs Annalen, vol. 391, pages 84-88 (1912). Compounds having the general formulae:

CH: H

wherein B, B1 and X have the meaning previously assigned to them and Z isa -S=O or by reaction with alkylene oxides such as ethylene oxide and propylene oxide, alkylene chlorohydrins such as ethylene chlorohydrin and propylene chlorohydrin and with alkyl halides such as methyl chloride, ethyl bromide and propyl chloride. Similarly, aryl groups can be introduced by arylation in known fashion. A

The azo dye compounds of our invention are, for the most part, relatively insoluble in water. Those compounds which are insoluble in water may be advantageously-employed for the direct dyeing of textile materials by grinding the dye to a fine powder, intimately mixing it with a suit! able dispersing or solubilizing agent, and adding the resulting mixture to. water or a dilute solution of soap in water to form an aqueous dyebath.

Following this known preparation of the dyebath,

cellulose textile materials from an aqueous solution of the dye which may contain salt. For a more complete description as to how the azo dye compounds of our invention may be employed in dyeing or coloring operations, reference maybe had to our U. S. Letters Patent No. 2,115,030,issued April 26, 1938. For a more detailed description as to how the water-soluble azo dyes of our invention may be employed for the coloration of textile materials made of or containing organic derivatives of cellulose, silk and wool or mixtures of these, reference may be had to our U. S. Letters Patent No. 2,107,898, issued February 8, 1938.

We claim:

- 1. The azo dye compounds selected from the group consisting of azo compounds having the general formulae:

H l RN=NB l x and /CE: /H z (ll-X RN=Ng NY B1 wherein R represents the residue of an aromatic nucleus, Z represents a member selected from the group consisting of a sulfur atom, a S=O group and a g group, B represents the residue of an aryl nucleus of the benzene series containing but one benzene nucleus and wherein the nitrogen atom shown and Z are attached to said aryl nucleus B in para and meta position, respectively, to the azo bond, B1 represents the residue of an aryl nucleus of the benzene series containing but one benzene nucleus joined to the nucleus shown through adjacent carbon atoms, X represents a member selected from the group consisting of hydrogen, an alkyl group, an allyl. group, and a cycloalkyl group and Y represents a member selected from the group consisting of hydrogen, an alkyl group, anallyl group, an aryl nucleus of the benzene series and a cycloalkyl group.

2. The azo dye compounds selected from the group consisting of azo'compounds having the general formulae:

and

group, B represents the residue of an aryl nucleus of the benzene series containing but one benzene nucleus and wherein the nitrogen atom and the sulfur atom shown are attached to said aryl nucleus B in para and meta position, respectively, to the azo bond, B1 represents the residue of an aryl nucleus of the benzene series containing but one benzene nucleus joined to the nucleus shown through adjacent carbon atoms, X represents a member selected from the group consisting of hydrogen, an alkyl group, an allyl group, and a cycloalkyl group and Y represents a member selected from the group consisting of hydrogen, an alkyl group, an allyl group, an aryl nucleus of the benzene series and a cycloalkyl group.

3. The azo dye compounds selected from the group consisting of azo compounds having the general formulae:

and

wherein R represents the residue of an aryl nucleus of the benzene series, B represents the residue of an aryl nucleus of the benzene series containing but one benzene nucleus and wherein the nitrogen atom and the sulfur atom shown are attached to said aryl nucleus B in para and meta position respectively to the azo bond, 31 represents the residue of an aryl nucleus of the benzene series containing but one benzene nucleus joined to the nucleus shown through adjacent carbon atoms, X represents a member selected from the group consisting of hydrogen, an alkyl group, an allyl group, and a cycloalkyl group and Y represents a member selected from the group consisting of hydrogen, an alkyl group, an allyl group, an aryl nucleus of the benzene series and a cycloalkyl group.

4. The azo dye compounds selected from the general formulae:

and

wherein R represents the residue of an aryl nucleus of the benzene series, B represents the residue of an aryl nucleus of the benzene series containing but one benzene nucleus and wherein the nitrogen atom and the sulfur atom shown are attached to said aryl nucleus B in para and meta position respectively to the azo bond, B1 represents the residue of an aryl nucleus ofthe benzene series containing but one benzene nucleus joined to the nucleus shown through adjacent carbon atoms, X represents a member selected from the group consisting of hydrogen, an alkyl group, an allyl group, and a cycloalkyl group and Y represents a member selected from the group consisting of hydrogen, an alkyl group, an allyl group, an aryl nucleus of the benzene series and a cycloalkyl group.

5. The azo dye compounds selected from the group consisting of azo compounds having the general formulae:

atoms, X represents a member selected from the group consisting of hydrogen,-an alkyl group, an allyl group, and a cycloalkyl group and Y represents a member selected from the group consisting of hydrogen, an alkyl group, an allyl group, an aryl nucleus of the benzene series and a cycloalkyl group.

6. The azo dye compounds selected from the group consisting of azo compounds having the general formulae:

Z-CH2 and 2GB: /H Z group consisting wherein R represents the residue of an aryl "nucleus of the benzene series, Z represents a member selected fromthe group consisting of a sulfur atom, a S=O group and a O group,;Xrepresents a member selected from the of hydrogen, an alkyl group, an allyl group, and a cycloalkyl group and Y represents a member selected from the group consisting of hydrogen, an alkyl group, an allyl group, an aryl nucleus of the benzene series and a cycloalkyl group.

7. The azo dye compounds having the general formula:

member selected from the group consisting of a sulfur atom, a S= group and a 7K group, B represents the residue of an aryl nucleus of the benzene series containing but one benzene nucleus and wherein the nitrogen atom shown and Z are attached to said aryl nucleus B in para and meta position respectively to the azo bond, X represents a member selected from the group consisting of hydrogen, an alkyl group, an allyl group, and a cy-cloalkyl group and Y represents a member selected from the group consisting of hydrogen, an alkyl group, an allyl group, an aryl nucleus of the benzene series and a cycloalkyl group.

8. The azo dye compounds having the general formula:

CH2 E wherein R represents the residue of anaryl nucleus of the benzene series, Z representsamember selected from the group consisting of a sulfur atom, a S=O group and a group, B1 represents the residue of an aryl nucleus of the benzene series containing but one benzene nucleus joined to the nucleus shown wherein R represents the residue of an aryl nucleus of the benzene series, Z represents a member selected from the group consisting of a sulfur atom, a -S=O group and a group, B represents the residue of an aryl nucleus of the benzene series containing but one benzene nucleus and wherein thenitrOgen atom shown and Z are attached to said aryl nucleus B in para and meta position, respectively, to the azo bond, B1 represents the residue of an aryl nucleus of the benzene series containing but one benzene nucleus joined to the nucleus shown through adjacent carbon atoms and wherein a hydrogen atom attached to the carbon atom numbered 3 and the hydrogen atom attached to the nitrogen atom numbered 4 can each be replaced by an alkyl group.

10. Material made of or containing an organic derivative of cellulose colored with a nuclear nonsulfonated azo dye compound selected from the group consisting of azo compounds having the general formulae:

and

wherein R represents the residue of an aromatic nucleus, Z represents a member selected from the group consisting of a sulfur atom, a S=O group and a group, B represents the residue of an aryl nucleus of the benzene series containing but one benzene nucleus and wherein the nitrogen atom shown and Z are attached to said aryl nucleus B in para and meta position, respectively/to the azo bond, B1 represents the residue of an aryl nucleus of the benzene series containing but one benzene nucleus joined to the nucleus shown through adjacent carbon atoms, X represents a member selected from the group consisting of hydrogen, an alkyl group, an allyl group, and a cycloalkyl group and Y represents a member selected from the group consisting of hydrogen, an alkyl group, an allyl group, an aryl nucleus of the benzene series and a cycloalkyl group.

11. Material made of orcontaining an organic derivative of cellulose colored with a nuclear nonsulfonated azo dye compound selected. from the group consisting of azo compounds having the lay group, B represents the residue of an aryl nucleus of the benzene series containing but one 0 benzene nucleus and wherein the nitrogen atom shown and Z are attached to said aryl nucleus B in para and meta position, respectively, to the azo bond, B1 represents the residue of an aryl nucleus of the benzene series containing but one benzene nucleus joined to the nucleus shown through adjacent carbon atoms, X represents a member selected from the group consisting of hydrogen, an alkyl group, an allyl group, and a cycloalkyl group and Y represents a member selected from the group consisting of hydrogen, an alkyl group, an allyl group, an aryl nucleus of the benzene series and a cycloalkyl group.

12. A cellulose acetate colored with a nuclear non-sulfonated azo dyecompound selected from the group consisting of azo compounds having the general formulae:

I Z- Hg and CH2 H wherein Rrepresents the residue of an aryl nucleus of the benzene series, Z represents a member selected from the group consisting of a sulfur atom, a S=O group and a p group, B represents the residue of an aryl nucleus of the benzene seriesv containing but one benzene nucleus and wherein the nitrogen atom shown and Z are attached tosaidaryl nucleus 13 in para and meta position, respectively to the azo bond, B1 represents the residue of an aryl nucleus of the benzene series containing but one an alkyl group, an allyl group, an aryl nucleus of the benzene series and a cycloalkyl group.

13. A cellulose acetate colored with a nuclear non-sulfonated azo dye compound selected from the group consisting of azo compounds having the general formulae:

wherein R represents the residue of an aryl nucleus of the benzene series, Z represents a memher selected from the group consisting of a sulfur atom, a S=O group and a S\ p o v h group, B represents the residue of an aryl nucleus of the benzene series containing but one benzene nucleus and wherein the nitrogen atom shown and Z are attached to said aryl nucleus B in para and meta position, respectively, to the azo bond, 131 represents the residue of an aryl nucleus of the benzene series containing but one benzene nucleus joined to the nucleus shown through adjacent carbon atoms and wherein a hydrogen atom attached to the carbon atom numbered 3 and the hydrogen atom attached to the nitrogen atom numbered 4 can each be replaced by an alkyl group.

JAMES G; McNALLY.

JOSEPH B. DICKEY. 

